The Raman spectra of mixed crystals of [(NH4)1−x Kx]2 SO4 in the region 50–3400 cm−1 at 293 K and below 223 K have been reported. At room temperature 293 K, as the concentration of K+ ion increases in the crystal up to 50%, the frequencies of the totally symmetric vibrations of SO42− and NH4+ ions increase and thereafter the frequency of SO42− vibration decreases and attains the value in K2SO4. This change in frequency up to 50% of potassium concentration is due to the breaking of hydrogen bonds of the type N-H...O. The behaviour of Raman intensities of Ag(v1) mode of SO42− for various concentrations (x=0, 0·03, 0·11, 0·5, 0·85) suggest that the phase transition changes from first order type to one of second order. The phase transition in mixed crystals of [(NH4)1−x Kx]2 SO4 can be a cooperative phenomenon arising from a coupling between (NH4)+ ions through hydrogen bonds with the distorted SO42− ions in the low temperature phase.
Volume 96, 2022
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